Hydroxy-peroxides and their uses

ABSTRACT

Novel hydroxy peroxides of the Structure A HO-R11-X-OO-R (A) [wherein R-, -R11- and -X- are as defined in the Summary of the Invention Section], having 10 hour half-life temperatures of 85 DEG -100 DEG  C., the processes for their preparation, and the use of these novel compositions in curing of unsaturated polyester resins and in initiating polymerization of ethylenically unsaturated monomers.

This is a divisional of copending application Ser. No. 08/001,921 filedon Jan. 8, 1993, now U.S. Pat. No. 5,304,649.

BACKGROUND OF THE INVENTION

This invention relates to novel hydroxy-peroxides of the Structure A:

    HO--R.sub.11 --X--OO--R                                    (A)

[wherein R--, --R₁₁ -- and --X-- are as defined in the Summary of theInvention Section] having 10 hour half-life temperatures of 85°-110° C.,the processes for their preparation, and the use of these novelcompositions in curing of unsaturated polyester resins and in initiatingpolymerization of ethylenically unsaturated monomers.

PRIOR ART

In applicant's opinion, the closest prior art to this invention includesU.S. Pat. No. 3,236,872 which discloses hydroxy-peroxides of thestructure: ##STR1## (wherein R-- is hydrogen, an acyl, an aroyl or alkylgroup, especially the t-butyl group, t-amyl or the hexylene glycolresidue; R'-- is hydrogen or an acyl, aroyl or alkyl group.)

The only acyl or aroyl groups specifically illustrated were acetyl andbenzoyl. Additional close prior art includes U.S. Pat. Nos. 4,525,308,and 4,634,753 which disclose hydroxy-peroxyesters having 10 hourhalf-life temperatures below about 75° C. This art does not cover thecompositions of the present invention which have 10 hour half-lifetemperatures of 85°-110° C.

U.S. Pat. No. 3,671,651 (col 8, lines 1 and 2) discloses ahydroxy-peroxyester, t-butyl peroxy-(3-hydroxypropionate). U.S. Pat. No.4,115,455 discloses the preparation of hydroxy-dialkyl peroxides bymeans of either catalytic hydrogenation of carbonyl-containing peroxidesor by treatment of carbonyl-containing peroxides with an alkali aluminumhydride or an alkali boron hydride. U.S. Pat. No. 3,576,826 disclosesprocesses for preparing ether-peroxy compounds by the uncatalyzedaddition of t-alkyl hydroperoxides to alpha-substituted vinyl ethers.

U.S. Pat. No. 4,180,518 discloses monoperoxycarbonates andperoxycarbamates of the structure ##STR2## where R₄ -- is t-alkyl of 4to 10 carbons, t-aralkyl of 9-16 carbons, t-cycloalkyl of 6 to 12carbons, ##STR3## and Z-- is ##STR4## The hydroxy-monoperoxycarbonatesof the instant invention are not disclosed by U.S. Pat. No. 4,180,518since this patent does not disclose that Z-- is HO--.

The novel hydroxy-peroxides of the instant invention possess reactivehydroxy functions in addition to the peroxide functions. Peroxides withreactive functional groups are known in the literature and several aresold commercially. Commercially produced peroxides with reactivefunctional groups include succinic acid peroxide (carboxy groups) andOO-t-butyl O-hydrogen monoperoxymaleate (carboxy group). More recently,3-hydroxy-1,1-dimethylbutyl peroxy-2-ethylhexanoate (hydroxy group) and3-hydroxy-1,1-dimethylbutyl peroxyneoheptanoate (hydroxy group) havebeen offered commercially. Other reactive initiators are disclosed inthe literature. U.S. Pat. No. 3,236,872 discloses hydroxy-hydroperoxidesand hydroxy-dialkyl peroxides, U.S. Pat. No. 3,991,085 disclosesepoxy-peroxides, U.S. Pat. No. 3,660,468, U.S. Pat. No. 3,671,651 andU.S. Pat. No. 3,952,041 disclose peroxides with reactive acid chloride,chloroformate, anhydride and/or carboxy groups. Such functionalizedinitiators enable polymer producers to enhance the utility and value ofpolymers by allowing them to `put` the reactive groups onto polymers bymeans of free-radical polymerization of ethylenically unsaturatedmonomers or by means of grafting reactions using these reactive peroxideinitiators.

Thus, there is a need in the polymer industry for reactivefunctionalized initiators (peroxides and azos) which can be used toproduce reactive, functionalized polymers or peroxy-polymers by variousmeans such as free-radical polymerization of ethylenically unsaturatedmonomers, grafting onto polymers, chain termination of condensationpolymers, reaction with co-functionalized polymers, etc. When theinitiator group of the functionalized initiator decomposes in theseprocesses, polymers with functional groups (i.e., at chain ends orpendant) are produced. Such polymers can be chain extended to producedesirable high performance polymers. This technique is the basis for thehigh solids acrylic coatings business in which hydroxy-containing lowmolecular weight acrylic copolymers are chain extended/cross linked withco-reactive compounds after being applied in automotive coatingsapplications. When the reactive functional initiator is used to chainterminate condensation polymers or to react with co-reactive polymers,polymers with initiator end groups and/or pendant initiator groups areproduced. These peroxy-polymers can then be used to produce block orgraft Copolymers that can be used in compatibilizing polymer blends andalloys produced from incompatible polymers. Hydroxy-peroxides haveutility in the above applications.

There are a number of hydroxy-peroxides described in the art. U.S. Pat.No. 4,525,308 and U.S. Pat. No. 4,634,753 describe and disclosehydroxy-peroxyesters having 10 hour half-life temperatures (i.e., thetemperature at which the half-life of the initiator is 10 hours) below75° C. These peroxides find use in vinyl chloride polymerizations andcopolymerizations and in lower temperature ethylene polymerizations andcopolymerizations. U.S. Pat. No. 3,236,872 discloseshydroxy-hydroperoxides and hydroxy-dialkyl peroxides which have 10 hourhalf-life temperatures above about 120° C. These peroxides find use inhigher temperature applications such as polyethylene crosslinking andpolypropylene modification. There is a need in the polymer industry forhydroxy-initiators which have 10 hour half-life temperatures between 75°C. and 120° C. for use in preparing polystyrenes, polyacrylates andother polymers with hydroxy end groups for subsequent reactions. U.S.Pat. No. 3,671,651 discloses a hydroxy-peroxyester, t-butylperoxy-3-hydroxypropionate, which is estimated to have a 10 hourhalf-life temperature of about 100° C., right in the middle of thedesirable temperature range of 75° C. to 120° C. However, the product isdifficult to prepare and the substrate employed in its synthesis,beta-propiolactone, is a highly toxic cancer suspect agent. On the otherhand, the hydroxy-peroxides of the instant invention have 10 hourhalf-life temperatures in the desirable 85° C. to 110° C. temperaturerange, are relatively easy to prepare and are prepared from relativelynon-toxic starting materials. Hence, they satisfy a need and advance thepolymerization art.

Some of the hydroxy-peroxides of this invention were prepared byreacting hydroxy-hydroperoxides with certain hindered substitutedbenzoyl halides. This result was unexpected in view of the art,especially U.S. Pat. No. 3,236,872. claim 1 of U.S. Pat. No. 3,236,872broadly covers hydroxy-peroxides including hydroxy-peroxyesters. Theexamples of U.S. Pat. No. 3,236,872 teach that reactions of benzoylchloride and acetyl chloride with hydroxy-hydroperoxides (such as3-hydroxy-1,1-dimethylbutyl hydroperoxide) result in acylation at boththe hydroxy group as well as at the hydroperoxy group resulting in theformation of a benzoate-peroxybenzoate with benzoyl chloride (Example 3)and an acetate-peroxyacetate with acetyl chloride (Example 6). Accordingto Example 11 of the instant invention, reaction of benzoyl chloridewith excess 3-hydroxy-1,1-dimethylbutyl hydroperoxide resulted information of 3-benzoyloxy-1,1-dimethylbutyl peroxybenzoate (C-1a) ratherthan in formation of 3-hydroxy-1,1-dimethylbutyl peroxybenzoate (C-1).Even the skewing of the process conditions in favor of formation of C-1,by employing excess 3-hydroxy-1,1-dimethylbutyl hydroperoxide, failed toresult in formation of C-1, but instead, C-1a was formed. Thus, U.S.Pat. No. 3,236,872 does not teach one skilled in the art how to makehydroxy-peroxyesters from 3-hydroxy-1,1-dimethylbutyl hydroperoxide andbenzoyl chlorides.

We surprisingly found that, under essentially the same processconditions as employed in Example 11 of the instant invention, hinderedbenzoyl chlorides, such as 2-chlorobenzoyl chloride, 2-methylbenzoylchloride, 2-bromobenzoyl chloride and others, resulted in formation ofthe corresponding hydroxyalkyl substituted-peroxybenzoates (seeCompositions I-7, I-8, I-9 and I-10, Examples 7, 8, 9 and 10).

SUMMARY OF THE INVENTION

This invention provides for novel hydroxy-peroxides, having 10 hourhalf-life temperatures of 85°-110° C., having Structure A:

    HO--R.sub.11 --X--OO--R                                    (A)

where --X-- can be a direct bond or the diradical, ##STR5## and,

I. when --X-- is a direct bond,

R-- is selected from the structures, ##STR6## where R₁ -- is a loweralkyl radical of 1 to 4 carbons, an alkoxy radical of 1 to 4 carbons, aphenyl radical, an acyloxy radical of 2 to 8 carbons, at-alkylperoxycarbonyl radical of 5 to 9 carbons, hydroxy, fluoro, chloroor bromo, R'₁ -- is hydrogen or is selected from the same radicals as R₁--, and can be the same as or different than R₁ --, and, n is 0 or 1, R₂-- is a substituted or unsubstituted alkyl radical of 1 to 18 carbons,substituents being one or more alkyl radicals of 1 to 6 carbons,t-alkylperoxy radicals of 4 to 8 carbons, alkoxy radicals of 1 to 6carbons, aryloxy radicals of 6-10 carbons, hydroxy, chloro, bromo orcyano or a substituted or unsubstituted cycloalkyl radical of 5 to 12carbons optionally having one or more oxygen or nitrogen atoms in thecycloalkane ring, with substituents being one or more lower alkylradicals of 1 to 4 carbons, or R₂ -- can be the radical, ##STR7## wherez is 0 or 1, R₁ --, R_(b) -- and R_(c) -- are the same or different andare hydrogen or alkyl radicals of 1 to 8 carbons, with the furtherproviso that R_(a) and R_(b) can be connected forming a substituted orunsubstituted ring containing 5-12 carbons, substituents being one ormore alkyl radicals of 1 to 5 carbons or phenyl radicals, --R₂₂ -- is asubstituted or unsubstituted alkylene diradical of 2 to 3 carbons,substituents being one or more lower alkyl radicals of 1 to 4 carbons,or a substituted or unsubstituted 1,2-phenylene diradical, substituentsbeing one or more lower alkyl radicals of 1 to 4 carbons, chloro, bromo,nitro or carboxy, and,

R₃ -- is a lower alkyl radical of 1 to 4 carbons, and, additionally, thetwo R₃ -- radicals can be connected together forming a ring containing 5to 6 carbons, and, R₄ -- is a lower alkyl radical of 1 to 4 carbons,and,

the --R₁₁ -- diradical is the structure, ##STR8## where R₅ -- is a loweralkyl radical of 1 to 4 carbons, and --R₃₃ -- is a substituted orunsubstituted alkylene diradical of 2 to 4 carbons, substituents beingone or more lower alkyl radicals of 1 to 4 carbons, and,

II. when --X-- is the diradical ##STR9## --Y-- is --O-- or --NR₆ --,where R₆ -- is hydrogen or a substituted or unsubstituted alkyl radicalof 1 to 8 carbons, substituents being one or more lower alkyl radicalsof 1 to 4 carbons or hydroxy, and, R₂₂ -- has the same definition aswhen --X-- is a direct bond, and,

R-- can be a substituted or unsubstituted t-alkyl radical of 4 to 12carbons, substituents being lower alkyl radicals of 1 to 4 carbons ort-alkylperoxy radicals of 4 to 8 carbons, a t-cycloalkyl radical of 6 to13 carbons, a t-alkynyl radical of 5 to 8 carbons, or a t-aralkylradical of 9 to 13 carbons, and,

--R₁₁ -- can be a substituted or unsubstituted alkylene diradical of 2to 8 carbons, optionally possessing one or more oxygen or nitrogenheteroatoms in the alkylene chain, substituents being one or more loweralkyl radicals of 1 to 4 carbons, lower hydroxyalkyl radicals of 1 to 4carbons or hydroxy.

The invention also provides for novel processes using the novelhydroxy-peroxides of Structure A as curing agents for the curing ofunsaturated polyester resin compositions by heating such resins in thepresence of initiating amounts of the novel hydroxy-peroxides ofStructure A at appropriate temperatures.

The invention still further provides novel processes using the novelhydroxy-peroxides of Structure A as free radical initiators forpolymerizing ethylenically unsaturated monomers (such as styrene,ethylene etc.) by the use of initiating amounts of the novelhydroxy-peroxides of Structure A at appropriate temperatures.

DETAILED DESCRIPTION OF THE INVENTION PREPARATIONS OF THE NOVELHYDROXY-PEROXIDES

The types of novel hydroxy-peroxides of this invention include severaltypes of peroxides when --X-- of Structure A is a direct bond. Theseinclude hindered hydroxy-peroxyesters, i.e. , where R-- is: ##STR10##OO-hydroxyalkyl O-alkyl monoperoxydicarboxylates, i.e., where R-- is:##STR11## and n is 1, hydroxy-monoperoxycarbonates, i.e., where R-- is:##STR12## and n is 0, and hydroxy-monoperoxyketals, i.e., where R-- is:##STR13## The types of novel hydroxy-peroxides of this invention alsoinclude hydroxy-peroxyesters when --X-- of Structure A is: ##STR14## Thenovel hindered hydroxy-peroxyesters of Structure A can be prepared byreacting acid halides of Structure B (where Q-- is Cl-- or Br--)##STR15## with hydroxy-hydroperoxides of Structure C

    HO--R.sub.11 --OO--H                                       (C)

in the presence of an organic or inorganic base. Acid halides ofStructure B include, without limiting, 2-methylbenzoyl chloride,2-ethylbenzoyl chloride, 2-methoxybenzoyl chloride, 2,6-dimethylbenzoylchloride, 2-phenylbenzoyl chloride, 2-chlorobenzoyl chloride,2,4-dichlorobenzoyl chloride, 2-bromobenzoyl chloride, 2-bromobenzoylbromide, 2-fluorobenzoyl chloride, 2-acetoxybenzoyl chloride, and2-(t-butylperoxycarbonyl)benzoyl chloride.

Non-limiting examples of hydroxy-hydroperoxides of Structure C include3-hydroxy-1,1-dimethylpropyl hydroperoxide, 3-hydroxy-1,1-dimethylbutylhydroperoxide and 4-hydroxy1,1-dimethylbutyl hydroperoxide.

Inorganic bases that are useful in the novel synthetic processes of thisinvention include sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium hydroxide, potassium carbonate, potassium hydrogencarbonate, calcium hydroxide, barium hydroxide, calcium carbonate andtrisodium phosphate. Non-limiting examples of organic bases useful forpreparing the hydroxy-peroxides of this invention includetrimethylamine, triethylamine, tri-n-butylamine,1,4-diazabicyclo[2.2.2]octane, pyridine, N,N-dimethylaniline,N,N-diethylaniline, p-N,N-dimethylaminopyridine and methylpyridines.

The novel OO-hydroxyalkyl O-alkyl monoperoxydicarboxylates of StructureA can be prepared by reacting an acid halide of Structure D ##STR16##with a hydroxy-hydroperoxide of Structure C in the presence of anorganic or inorganic base. Acid halides of Structure D include2-methoxycarbonylbenzoyl chloride, 2-n-butoxycarbonylbenzoyl chloride,2-(2-ethylhexoxycarbonyl)benzoyl chloride, 2-cyclohexoxycarbonylbenzoylchloride, 2-(4,4-dimethyl-3,5dioxacyclohexoxycarbonyl)benzoyl chloride,2-[(1,4,4-trimethyl-3,5-dioxacyclohexyl)methoxycarbonyl]benzoylchloride, 2-[(3,3-dimethyl-2,4-dioxacyclopentyl)methoxycarbonyl]benzoylchloride, 2-[(2,4-dioxacyclopentyl)methoxycarbonyl]benzoyl chloride,3-methoxycarbonylpropionyl chloride, 4-butoxycarbonylbutyryl chloride,3-(4,4-dimethyl-3,5-dioxacyclohexoxycarbonyl)propionyl chloride,3-(3,5-dioxacyclohexoxycarbonyl)propionyl chloride,4-[(1,4,4-trimethyl-3,5-dioxacyclohexyl)methoxycarbonyl]butyrylchloride,3-[(3,3-dimethyl-2,4-dioxacyclopentyl)methoxycarbonyl]propionyl chlorideand 3,4,5,6-tetrachloro-2-methoxycarbonylbenzoyl chloride.

The acid halides of Structures B and D can be prepared by treating thecorresponding carboxylic acids with acid halogenating agents such asPCl₃, POCl₅, PCl₅, thionyl chloride, thionyl bromide, phosgene (in thepresence of dimethylformamide, DMF), benzotrichloride and others.

The novel hydroxy-monoperoxycarbonates of Structure A can be prepared byreacting alkyl haloformates of structure E ##STR17## withhydroxy-hydroperoxides of Structure C in the presence of an organic orinorganic base.

Alkyl haloformates of Structure E include methyl chloroformate, ethylchloroformate, isopropyl chloroformate, isopropyl bromoformate, butylchloroformate, 2-butyl chloroformate, neopentyl chloroformate,2-ethylhexyl chloroformate, 2-ethylbutyl chloroformate, 2-butyloctylchloroformate, 4-methyl-2-pentyl chloroformate, dodecyl chloroformate,hexadecyl chloroformate, 2-chloroethyl chloroformate, 2-butoxyethylchloroformate, 2-phenoxyethyl chloroformate, cyclohexyl chloroformate,4-t-butylcyclohexyl chloroformate, 3,3,5-trimethylcyclohexylchloroformate, cyclododecyl chloroformate,2,2,6,6-tetramethyl-4-piperidinyl chloroformate (and hydrochloridesalt), 1,2,2,6,6-pentamethyl-4-piperidinyl chloroformate (andhydrochloride salt), (3,3-dimethyl-2,4-dioxacyclopentyl)methylchloroformate, (2,4-dioxacyclopentyl)methyl chloroformate,(4,4-dimethyl-3,5-dioxacyclohexyl) chloroformate,(3,5-dioxacyclohexyl)chloroformate,(1,4,4-trimethyl-3,5-dioxacyclohexyl)methyl chloroformate and1,3-dimethyl-3-(t-butylperoxy)butyl chloroformate.

The alkyl haloformates of Structure E can be prepared by reacting thecorresponding alcohols with excess phosgene.

The novel hydroxy-monoperoxyketals of this invention can be prepared byreacting alpha-substituted vinyl ethers of Structure F: ##STR18## (whereR'₃ -- is hydrogen or an alkyl radical of 1 to 3 carbons, and R₃ -- andR'₃ -- can be connected together to form a ring containing 5 to 6carbons) with hydroxy-hydroperoxides of Structure C in the absence ofany catalyst.

Non-limiting examples of alpha-substituted vinyl ethers of Structure Finclude methyl isopropenyl ether, ethyl isopropenyl ether, n-butylisopropenyl ether, 1-methoxy-1-cyclohexene, 1-ethoxy-1-cyclohexene and1-methoxy-3,3,5-trimethylcyclohexene.

When --X-- of Structure A is the diradical ##STR19## the novelhydroxy-peroxyesters of Structure A can be prepared by reactingt-alkylperoxycarbonyl substituted acyl halides of Structure G ##STR20##with di- or polyols or amino-alcohols of Structure H

    HO--R.sub.11 --Y--H                                        (H)

Non-limiting examples of the t-alkylperoxycarbonyl substituted acylhalides of Structure G include 2-(t-butylperoxycarbonyl)benzoylchloride, 2-(t-amylperoxycarbonyl)benzoyl chloride,3-(t-butylperoxycarbonyl)propionyl chloride,3-(t-amylperoxycarbonyl)propionyl chloride and4-(t-butylperoxycarbonyl)butyryl chloride.

These t-alkylperoxycarbonyl substituted acyl halides can be prepared ina two-step synthetic scheme involving initially formingt-alkylperoxycarbonyl substituted carboxylic acids via reaction oft-alkyl hydroperoxides with cyclic anhydrides followed by reaction ofthe t-alkylperoxycarbonyl substituted carboxylic acids with acidchlorinating agents such as thionyl chloride.

Di- or polyols or amino-alcohols of Structure H include ethylene glycol,diethylene glycol, 1,2- and 1,3-propanediols, dipropylene glycol, 1,2-,1,3- and 1,4-butanediols, 1,4-butynediol, 2,2-dimethyl-1,3-propanediol,2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, glycerol,trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol,ethanolamine, diethanolamine, propanolamine, dipropanolamine,N-methylethanolamine and N-ethylethanolamine.

Novel Hydroxy-Peroxides

Representative hindered hydroxy-peroxyesters of this invention when--X-- of Structure A is a direct bond include3-hydroxy-1,1-dimethylpropyl peroxy-(2-chlorobenzoate),3-hydroxy-1,1-dimethylbutyl peroxy-(2-methylbenzoate),3-hydroxy-1,1-dimethylbutyl peroxy-(2,4-dimethylbenzoate),3-hydroxy-1,1-dimethylbutyl peroxy-(2,6-dimethylbenzoate),3-hydroxy-1,1-dimethylbutyl peroxy-(2-fluorobenzoate),3-hydroxy-1,1-dimethylbutyl peroxy-(2-chlorobenzoate),3-hydroxy-1,1-dimethylbutyl peroxy-(2-bromobenzoate),3-hydroxy-1,1-dimethylbutyl peroxy-(2,4-dichlorobenzoate),3-hydroxy-1,1-dimethylbutyl peroxy-(2-phenylbenzoate),3-hydroxy-1,1-dimethylbutyl peroxy-(2-methoxybenzoate),3-hydroxy-1,1-dimethylbutyl peroxy-(2-acetoxybenzoate).

Representative OO-hydroxyalkyl O-alkyl monoperoxydicarboxylates of thisinvention include OO-(3-hydroxy-1,1-dimethylbutyl) O-methylmonoperoxyphthalate, OO-(3-hydroxy-1,1-dimethylbutyl) O-n-butylmonoperoxyphthalate, OO-(3-hydroxy-1,1-dimethylbutyl)O-[(2,4-dioxacyclopentyl)methyl]monoperoxyphthalate (a),O-(3-hydroxy-1,1-dimethylbutyl)O-[(3,3-dimethyl-2,4-dioxacyclopentyl)methyl]monoperoxyphthalate (b),OO-(3-hydroxy-1,1-dimethylbutyl)O-[(4,4-dimethyl-3,5-dioxacyclohexyl)methyl]monoperoxysuccinate (e),O-[(1,4,4-trimethyl-3,5-dioxacyclohexyl)methyl]monoperoxyglutarate (d),OO-(3-hydroxy-1,1-dimethylbutyl) O-(2,3-dihydroxypropyl)monoperoxy-phthalate (e), OO-(3-hydroxy-1,1-dimethylbutyl)O-(1,3-dihydroxy-2-propyl) monoperoxysuccinate (f) andOO-(3-hydroxy-1,1-dimethylbutyl)O-(3-hydroxy-2-hydroxymethyl-2-methylpropyl) monoperoxyglutarate (g).Compositions (e), (f) and (g) are preparable by treating compositions(a) [or (b)], (c) and (d), respectively, with dilute aqueous mineralacid solution and isolating compositions (e), (f) and (g) byneutralizing with inorganic bases, separating off the neutralizationsalt and removing water by stripping in vacuo. Non-limiting examples ofmineral acids useful for preparations of (e), (f) and (g) include HCl.HBr, HNO₃, H₂ SO₄, NaHSO₄, H₃ PO₄ and others. Non-limiting examples ofinorganic bases useful for preparations of (e), (f) and (g) include KOH,NaOH, Ca(OH)₂, NaHCO₃, Na₂ CO₃, K₂ CO₃ and others.

Hydroxy-monoperoxycarbonates of this invention includeOO-(3-hydroxy-1,1-dimethylpropyl) O-(2-ethylhexyl)monoperoxycarbonate,OO-(3-hydroxy-1,1-dimethylbutyl) OO-isopropyl monoperoxycarbonate,OO-(3-hydroxy-1,1-dimethylbutyl) O-(2-butyl) monoperoxycarbonate,OO-(3-hydroxy-1,1-dimethylbutyl) O-(2-ethylhexyl) monoperoxycarbonate,OO-(3-hydroxy-1,1-dimethylbutyl) O-(2-butyloctyl) monoperoxycarbonate,OO-(3-hydroxy-1,1-dimethylbutyl) O-cyclohexyl monoperoxycarbonate,OO-(3-hydroxy-1,1-dimethylbutyl) O-cyclododecyl monoperoxycarbonate,OO-(3-hydroxy-1,1-dimethylbutyl) O-(4-t-butylcyclohexyl)monoperoxycarbonate, OO-(3-hydroxy-1,1-dimethylbutyl)O-(2,2,6,6-tetramethyl-4-piperidinyl) monoperoxycarbonate (and salts),OO-(3-hydroxy-1,1-dimethylbutyl)OO-(1,2,2,6,6-pentamethyl-4-piperidinyl) monoperoxycarbonate (andsalts), OO-(3-hydroxy-1,1-dimethylbutyl)O-(4,4-dimethyl-3,5-dioxacyclohexyl) monoperoxycarbonate (h),OO-(3-hydroxy-1,1-dimethylbutyl) O-(3,5-dioxacyclohexyl)monoperoxycarbonate (i), OO-(3-hydroxy-1,1-dimethylbutyl)O-[(3,3-dimethyl-2,4-dioxacyclopentyl)methyl]monoperoxycarbonate (j),OO-(3-hydroxy-1,1-dimethylbutyl)O-[(2,4-dioxacyclopentyl)methyl]monoperoxycarbonate (k),OO-(3-hydroxy-1,1-dimethylbutyl)O-[(1,4,4-trimethyl-3,5-dioxacyclohexyl)methyl monoperoxycarbonate (1),OO-(3-hydroxy-1,1-dimethylbutyl)O-(2,3-dihydroxypropyl)monoperoxycarbonate (m),OO-(3-hydroxy-1,1-dimethylbutyl) O-(1,3-dihydroxy-2-propyl)monoperoxycarbonate (n) and OO-(3-hydroxy-1,1-dimethylbutyl)O-(3-hydroxy-2-hydroxymethyl-2-methylpropyl)monoperoxycarbonate (o).Compositions (m), (n) and (o) are preparable by treating compositions(h) [or (i)], (j) [or (k)] and (l) , respectively, with dilute aqueousmineral acid solution and isolating compositions (m), (n) and (o) byneutralizing with inorganic bases, separating the neutralization saltand removing water by stripping in vacuo as described above.

Representative of hydroxy-monoperoxyketals of this invention include2-methoxy-2-(3-hydroxy-1,1-dimethylpropylperoxy) propane,2-methoxy-2-(3-hydroxy-1,1-dimethylbutylperoxy)propane and1-methoxy-1-(3-hydroxy-1,1-dimethylbutylperoxy)cyclohexane.

When --X-- of Structure A is the diradical ##STR21## novelhydroxy-peroxides of this invention include O-t-amylO-(2-hydroxyethyl)monoperoxyphthalate, OO-t-butyl O-(2-hydroxyethyl)monoperoxyphthalate, OO-t-butyl O-(2-hydroxypropyl) monoperoxyphthalate,OO-(1,1-dimethyl-2-propynyl) O-(2-hydroxypropyl) monoperoxyphthalate,OO-t-butyl O-(2-hydroxypropyl) monoperoxysuccinate, OO-t-butylO-(2-hydroxypropyl) monoperoxyglutarate, OO-(1,1,3,3-tetramethybutyl),O-(2-hydroxypropyl) monoperoxyphthalate, OO-t-butyl,O-(2,3-dihydroxypropyl) monoperoxyphthalate, OO-t-butyl,O-(2,2-di[hydroxymethyl]propyl) monoperoxyphthalate, N-(2-hydroxyethyl)2-(t-butylperoxycarbonyl)benzamide and N,N-di-(2-hydroxyethyl)2-(t-butylperoxycarbonyl)benzamide.

Polymerization of Ethylenically Unsaturated Monomers

In the free-radical polymerizations of ethylenically unsaturatedmonomers at suitable temperatures and pressures the novelhydroxy-peroxides of Structure A of this invention are found to beefficient initiators (reduced initiator requirements, etc.).Ethylenically unsaturated monomers include olefins, such as ethylene,propylene, styrene, alpha-methylstyrene, p-methylstyrene,chlorostyrenes, bromostyrenes, vinylbenzyl chloride, vinylpyridine anddivinylbenzene; diolefins, such as 1,3-butadiene, isoprene andchloroprene; vinyl esters, such as vinyl acetate, vinyl propionate,vinyl laurate, vinyl benzoate and divinyl carbonate; unsaturatednitriles, such as acrylonitrile and methacrylonitrile; acrylic acid andmethacrylic acid and their anhydrides, esters and amides, such asacrylic acid anhydride, methyl, ethyl, n-butyl, 2-hydroxyethyl, lauryland 2-ethylhexyl acrylates and methacrylates, and acrylamide andmethacrylamide; maleic anhydride and itaconic anhydride; maleic,itaconic and fumaric acids and their esters; vinyl halo and vinylidenedihalo compounds, such as vinyl chloride, vinyl bromide, vinyl fluoride,vinylidene chloride and vinylidene fluoride; perhalo olefins, such astetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene;vinyl ethers, such as methyl vinyl ether, ethyl vinyl ether and n-butylvinyl ether; allyl esters, such as allyl acetate, allyl benzoate, allylethyl carbonate, triallyl phosphate, diallyl phthalate, diallylfumarate, diallyl glutarate, diallyl adipate, diallyl carbonatediethylene glycol bis(allyl carbonate) (i.e., ADC); acrolein; methylvinyl ketone; or mixtures thereof.

Temperatures of 0° C. to 250° C., preferably 30° C. to 200° C., andhydroxy-peroxide levels (on a pure basis) of 0.002 to 3%, preferably0.002 to 1% by weight based on monomer, are normally employed inconventional polymerizations and copolymerizations of ethylenicallyunsaturated monomers. The novel hydroxy-peroxides of this invention canbe used in combination with other free-radical initiators such asperoxyesters which include t-butyl peroxypivalate, t-butylperoxy-2-ethylhexanoate, t-butyl peroxyacetate, t-butylperoxyneodecanoate, t-amyl peroxypivalate, t-amyl peroxyneodecanoate,1,1,3,3-tetramethylbutyl peroxyneodecanoate, and α-cumylperoxyneodecanoate; dialkyl peroxydicarbonates including di-n-propyl,diisopropyl, di-(sec-butyl), di-cyclohexyl, di-(4-t-butylcyclohexyl),di-(2-phenoxyethyl), di-(2-ethylhexyl) and dihexadecylperoxydicarbonates; acyl alkylsulfonyl peroxides including acetylcyclohexylsulfonyl peroxide, and acetyl sec-heptylsulfonyl peroxide;diacyl peroxides including dibenzoyl peroxide, didodecyl peroxide,diisobutyryl peroxide and di-(2-methylpentanoyl)peroxide; diperoxyketalsincluding 2,2-di-(t-butylperoxy)butane, 2,2-di-(t-butylperoxy)heptane,ethyl 3,3-di-(t-butylperoxybutyrate,1,1-di-(t-butylperoxy)-3,3,5-trimethylcyclohexane,1,1-di-(t-butylperoxy)cyclohexane and 1,1-di-(t-amyl peroxy)cyclohexane;monoperoxycarbonates including OO-t-butyl O-isopropylmonoperoxycarbonate and OO-t-butyl O-(2-ethylhexyl) monoperoxycarbonate;dialkyl peroxides such as 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane andazo compounds including azobis(isobutyronitrile),2-t-butylazo-2-cyano-4-methoxy-4-methylpentane and1-t-butylazo-1-cyanocyclohexane.

Using the hydroxy-peroxides of this invention in combination with theseinitiators adds flexibility to processes of polymer producers and allowsthem to fine their polymerization processes.

Curing of Unsaturated Polyester Resins

In the curing of unsaturated resin compositions by heating at suitablecuring temperatures in the presence of free-radical curing agents, thenovel hydroxy-peroxides of Structure A of this invention exhibitenhanced curing activity in the curable unsaturated polyester resincompositions.

Unsaturated polyester resins that can be cured by the novelhydroxy-peroxides of this invention usually include an unsaturatedpolyester and one or more ethylenically unsaturated monomers.

The unsaturated polyesters are, for instance, polyesters as they areobtained by esterifying at least one ethylenically unsaturated di- orpolycarboxylic acid, anhydride or acid halide, such as maleic acid,fumaric acid, glutaconic acid, itaconic acid, mesaconic acid, citraconicacid, allylmalonic acid, tetrahydrophthalic acid, and others, withsaturated and unsaturated di- or polyols, such as ethylene glycol,diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediols, 1,2-,1,3-and 1,4-butanediols, 2,2-dimethyl-1,3-propanediol,2-hydroxymethyl-2-methyl-1,3-propanediol, 2-buten-1,4-diol,2-butyn-1,4-diol, 2,4,4-trimethyl-1,3-pentanediol, glycerol,pentaerythritol, mannitol and others.

Mixtures of such di- or polyacids and/or mixtures of such di- or polyolsmay also be used. The di- or polycarboxylic acids may be partiallyreplaced by saturated di- or polycarboxylic acids, such as adipic acid,succinic acid, sebacic acid and other, and/or by aromatic di- orpolycarboxylic acids, such as phthalic acid, trimellitic acid,pyromellitic acid, isophthalic acid and terephthalic acid. The acidsused may be substituted by groups such as halogen. Examples of suchsuitable halogenated acids are tetrachlorophthalic acid,tetrabromophthalic acid,5,6-dicarboxy-1,2,3,4,7,7-hexachlorobicyclo(2.2.1)-2-heptene and others.

The other component of the unsaturated polyester resin composition, thepolymerizable monomer or monomers, can preferably be ethylenicallyunsaturated monomers, such as styrene, alpha-methylstyrene,p-methylstyrene, chlorostyrenes, bromostyrenes, vinylbenzyl chloride,divinylbenzene, diallyl maleate, dibutyl fumarate, triallyl phosphate,triallyl cyanurate, diallyl phthalate, diallyl fumarate, methylacrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate,ethyl acrylate, and others, or mixtures thereof, which arecopolymerizable with said unsaturated polyesters.

A preferred unsaturated polyester resin composition contains as theunsaturated polyester component the esterification product of1,2-propanediol (a polyol), maleic anhydride (an anhydride of anunsaturated polycarboxylic acid) and phthalic anhydride (an anhydride ofan aromatic dicarboxylic acid) as well as the monomer component,styrene.

Other types of unsaturated polyester resin compositions can be curedusing the novel hydroxy-peroxides of this invention as curing catalysts.These resins, called unsaturated vinyl ester resins, consist of a vinylester resin portion and one or more polymerizable monomer components.The vinyl ester resin component can be made by reacting a chloroepoxide,such as epichlorohydrin, with appropriate amounts of a bisphenol such asBisphenol A [2,2-di-(4-hydroxyphenyl)propane], in the presence of abase, such as sodium hydroxide, to yield a condensation product havingterminal epoxy groups derived from the chloroepoxide. Subsequentreaction of the condensation product with polymerizable unsaturatedcarboxylic acids, such as acrylic acid and methacrylic acid, in thepresence or absence of acidic or basic catalysts, results in formationof the vinyl ester resin component. Normally, styrene is added as thepolymerizable monomer component to complete the preparation of theunsaturated vinyl ester resin composition.

Temperatures of about 20° C. to 200° C. and hydroxy-peroxide levels ofabout 0.05% to 5% or more by weight of curable unsaturated polyesterresin composition are normally employed for curing of the unsaturatedpolyester resins.

The unsaturated polyester resin compositions described above can befilled with various materials, such as sulfur, glass, carbon and boronfibers, carbon blacks, silicas, metal silicates, clays, metalcarbonates, antioxidants (AO's), heat, ultraviolet (UV) and lightstabilizers, sensitizers, dyes, pigments, accelerators, metal oxides,such as zinc oxide, blowing agents, nucleating agents and others.

Curing of Elastomers and Crosslinking of Thermoplastic Polymers

In the curing of elastomeric compositions, and the crosslinking ofpolymer compositions, by heating at suitable curing and crosslinkingtemperatures in the presence of free-radical curing and crosslinkingagents, the novel hydroxy-peroxides of this invention exhibit curing andcrosslinking activities.

Elastomeric resin compositions that can be cured by the novelhydroxy-peroxides of this invention include elastomers such asethylene-propylene copolymers (EPR), ethylene-propylene-dieneterpolymers (EPDM), polybutadiene (PBD), silicone rubber (SR), nitrilerubber (NR), neoprene, fluoroelastomers and ethylene-vinyl acetatecopolymer (EVA).

Polymer compositions that can be crosslinked by the hydroxy-peroxides ofthis invention include olefin thermoplastics such as chlorinatedpolyethylene (CPE), low density polyethylene (LDPE), linear-low densitypolyethylene (LLDPE), and high density polyethylene (HDPE).

Temperatures of about 80° C. to 310° C. and hydroxy-peroxide levels ofabout 0.1% to 10%, preferably 0.5% to 5%, based on weight of curableelastomeric resin composition or cross-linkable olefin polymercomposition, are normally employed.

The curable elastomeric resin composition or cross-linkable polymercomposition can be optionally filled with the materials listed above foruse with the conventional unsaturated polyester resin compositions.

Modification of Propylene Homopolymers and Copolymers

In the processes for modifying propylene homopolymers, and, propylenecopolymers (e.g., beneficial degradation of polypropylene (PP) byreducing the polymer molecular weight and the polymer molecular weightdistribution), the novel hydroxy-peroxides of this invention exhibitpolypropylene modification activity.

Temperatures of about 140° C. to 340° C. and hydroxy-peroxide levels ofabout 0.01% to 1.0% based on weight of modifiable polyolefins orcopolymers are normally employed. Optionally, up to 1% by weight ofmolecular oxygen can be employed as a modification co-catalyst.

EXAMPLES EXAMPLE 1 Preparation of OO-(3-Hydroxy-1,1-dimethylbutyl)O-(2-Ethylhexyl) Monoperoxycarbonate (I-1)

A jacketed reactor equipped with a stirrer, a thermometer and anaddition funnel was charged with 40 mL of methylene chloride, 25.1 g(0.14 mole) of 74.9% 3-hydroxy-1,1-dimethylbutyl hydroperoxide and 39.2g (0.14 mole) of 20% aqueous KOH solution and the mixture was stirred at20° C. The liquid phases were allowed to separate and the lowermethylene chloride layer was removed. Then another 40 mL of methylenechloride was added, the mixture stirred at 20° C., the liquid layerssettled and the lower methylene chloride layer removed. Then thevigorously stirred aqueous solution was heated to 45° C. and to it,added rapidly over 4.5 minutes, was 19.3 g (0.10 mole) of 99%2-ethylhexyl chloroformate and the resulting mixture was stirred for anadditional 45 minutes at 45° C. The resulting vigorously stirred twophase liquid mixture was cooled to 20° C. and to it was added 80 mL ofpentane and 50 mL of water. Stirring was stopped and the lower aqueouslayer was removed and discarded. The pentane solution was then washed at20° C. with 50 mL portions of 10% aqueous KOH solution and then twicewith 50 mL portions of water. The pentane solution was then dried over10% by weight of anhydrous MgSO₄. After separation of the spentdesiccant by filtration, the pentane was removed in vacuo leaving 24.3 g(83.8% of theory, uncorrected) of a clear, colorless liquid. An infraredspectrum of the product showed a strong OH band at ca. 3410 cm-1, anunresolved double carbonyl band at ca. 1710 cm-1 and 1735 cm-1 and asmall --OO-- band at ca. 830 cm-1. These IR spectral bands correspondedto the desired structure and confirmed that the product was the titleproduct. The product had an Act[O] content of 4.71%. Based on atheoretical Act[O] of 5.51%, for the desired title product, the assaywas 85.5% and the corrected yield was 71.6%.

EXAMPLE 2 Preparation of OO-(3-Hydroxy-1,1-dimethylbutyl) O-(2-Butyl)Monoperoxycarbonate (I-2)

A jacketed reactor equipped with a stirrer, a thermometer and anaddition funnel was charged with 30 mL of methylene chloride, 16.6 g(0.093 mole) of 75.2% 3-hydroxy-1,1-dimethylbutyl hydroperoxide and 26.0g (0.093 mole) of 20% aqueous KOH solution and the mixture was stirredat 20° C. for 5 minutes. The liquid phases were allowed to separate andthe lower methylene chloride layer was removed. Then another 30 mL ofmethylene chloride was added, the mixture stirred at 20° C., the liquidlayers settled and the lower methylene chloride layer removed. Then thevigorously stirred aqueous solution was heated to 40°-45° C. and to it,added rapidly over 2.0 minutes, was 5.5 g (0.040 mole) of 99% 2-butylchloroformate and the resulting mixture was stirred for an additional 25minutes at 40°-45° C. The resulting vigorously stirred two phase liquidmixture was cooled to 20°-25° C. and to it was added 50 mL of pentane.Stirring was stopped and the lower aqueous layer was removed anddiscarded. The pentane solution was then washed twice at 20° C. with 50mL portions of 10% aqueous KOH solution and then three times with 70 mLportions of water. The pentane solution was then dried over 10% byweight of anhydrous MgSO₄. After separation of the spent desiccant byfiltration, the pentane was removed in vacuo leaving 3.9 g (41.5% oftheory, uncorrected) of a clear, colorless liquid. An infrared spectrumof the product showed a strong OH band at ca. 3410 cm-1, an unresolveddouble carbonyl band at ca. 1705 cm-1 and 1735 cm-1 and an --OO-- bandat ca. 865 cm-1. These IR spectral bands corresponded to the desiredstructure and confirmed that the product was the title product. Theproduct had an Act[O] content of 6.05%. Based on a theoretical Act[O] of6.83% for the desired title product, the assay was 88.6% and thecorrected yield was 36.8%

EXAMPLE 3 Preparation of OO-(3-Hydroxy-1,1-dimethylbutyl) O-IsopropylMonoperoxycarbonate (I-3)

A jacketed reactor equipped with a stirrer, a thermometer and anaddition funnel was charged with 30 mL of methylene chloride, 25.0 g(0.14 mole) of 75% 3-hydroxy-1,1-dimethylbutyl hydroperoxide and 39.2 g(0.14 mole) of 20% aqueous KOH solution and the mixture was stirred atca. 25° C. for 3 minutes. The liquid phases were allowed to separate andthe lower methylene chloride layer was removed. Then another 30 mL ofmethylene chloride wash was employed and the spent methylene chloridelayer was settled, separated and discarded. Then the vigorously stirredaqueous solution was heated to ca. 42°-48° C. and to it, added rapidlyover ca. 5 minutes, was 7.4 g (0.060 mole) of 98% isopropylchloroformate and the resulting mixture was stirred for an additional 35minutes at 45° C. after which 50 mL of water was added. The resultingvigorously stirred two phase liquid mixture was cooled to 20°-25° C. andto it was added 50 mL of pentane. Stirring was stopped and the loweraqueous layer was removed and discarded. The pentane solution was thenwashed twice at 20° C. with 50 mL portions of 10% aqueous KOH solutionand then washed to a pH of ca. 7 with 100 mL portions of water. Thepentane solution was then dried over 10% by weight of anhydrous MgSO₄.After separation of the spent desiccant by filtration, the pentane wasremoved in vacuo leaving 7.4 g (56.1% of theory, uncorrected) of aliquid product. An infrared spectrum of the product showed a strong OHband at ca. 3400 cm-1, a strong carbonyl band at ca. 1730 cm-1 (ashoulder at 1780 cm-1) and an --OO-- band at ca. 880 cm-1. These IRspectral bands corresponded to the expected IR spectrum of the desiredstructure and confirmed that the product was the title product. Theproduct had an Act[O] content of 6.65%. Based on a theoretical Act[O] of7.26% for the desired title product, the assay was 91.6% and thecorrected yield was 51.4%.

EXAMPLE 4 Preparation of OO-(3-Hydroxy-1,1-dimethylbutyl) O-CyclohexylMonoperoxycarbonate (I-4)

The apparatus and the procedure employed in Example 3 was used in thisexample. Reactants employed were 75% 3-hydroxy-1,1-dimethylbutylhydroperoxide (25.0 g; 0.14 mole), 20% aqueous KOH solution (39.2 g;0.14 mole) and 97.2% cyclohexyl chloroformate (10.0 g; 0.06 mole). Afterthe usual work-up, 11.8 g (75.6% of theory, uncorrected) of a liquidproduct was obtained. An infrared spectrum of the product showed astrong OH band at ca. 3400 cm-1, an unresolved double carbonyl band atca. 1700 cm-1 and 1720 cm-1 and a small --OO-- band at ca. 835 cm-1.These IR spectral bands corresponded to the desired structure andconfirmed that the product was the title product. The product had anAct[O] content of 5.45%. Based on a theoretical Act[O] of 6.15% for thedesired title product, the assay was 88.6% and the corrected yield was67.0%.

EXAMPLE 5 Preparation of OO-(3-Hydroxy-1,1-dimethylbutyl)O-(2,2,6,6-Tetramethyl-4-piperidinyl) Monoperoxycarbonate (I-5)

An Erlenmeyer flask was charged with 14.9 g (0.12 mole) of 45% aqueousKOH solution and 20 mL of water. The flask contents were cooled to 15°C. and 12.4 g (0.0694 mole) of 74.9% 3-hydroxy-1,1-dimethylbutylhydroperoxide was slowly added and allowed to stir for 5 minutes. Theflask contents were then transferred to a separatory funnel and werewashed with 25 mL of methylene chloride (poor separation) and with 15 mLof methyl t-butyl ether (better separation). The aqueous layer was thentransferred to a 3-neck round bottom flask and cooled to 10° C. Then 0.2g of N,N-dimethylaminopyridine (DMAP) was added and the solutionstirred. To this vigorously stirred solution at 10°-15° C. was slowlyadded 8.9 g (0.0315 mole) of2,2,6,6-tetramethyl-4-chlorocarbonyloxypiperidinium chloride over aperiod of about 30 minutes, however, the latter reactant did notdissolve readily, therefore, 30 mL of tetrahydrofuran (THF) was added.This appeared to facilitate the reaction. The reaction mixture was thenstirred for an additional 30 minutes at 10°-15° C., then for 120 minutesat 20°-25° C. Then 100 mL of methylene chloride was added, stirred andseparated. A second wash was carried out with a 50 mL portion ofmethylene chloride. The combined methylene chloride washes were thenwashed with 50 mL of 5% aqueous NaOH solution, with 50 mL of water,three times with 50 mL portions of saturated aqueous NaHSO3 solution andonce with 50 mL of 5% aqueous NaHCO₃ solution. The methylene chloridesolution was then dried over 10% by weight of anhydrous MgSO₄. Afterseparation of the spent desiccant by filtration, the solvent was removedin vacuo leaving 7.6 g (76% of theory, uncorrected) of white crystals,mp, 119°-27° C. The product had an Act[O] content of 4.47% and a3-hydroxy-1,1-dimethylbutyl hydroperoxide content of 1.6%. Based on atheoretical Act[O] of 7.26% for the desired title product and correctingfor the Act[O] due to 3-hydroxy-1,1-dimethylbutyl hydroperoxide, theassay of the product was 84.9% and the corrected yield was 64.5%.

EXAMPLE 6 Preparation of OO-(3-Hydroxy-1,1-dimethylbutyl)O-(2-Phenoxyethyl) Monoperoxycarbonate (I-6)

The apparatus and the procedure employed in Example 3 was used in thisexample. Reactants employed were 75% 3-hydroxy-1,1-dimethylbutylhydroperoxide (25.0 g; 0.14 mole), 20% aqueous KOH solution (39.2 g;0.14 mole) and 99% 2-phenoxyethyl chloroformate (12.2 g; 0.06 mole).After the usual work-up, 11.8 g (65.9% of theory, uncorrected) of astraw-color liquid product was obtained. An infrared spectrum of theproduct showed an OH band at ca. 3380 cm-1, a strong carbonyl band atca. 1730 cm-1 and a small --OO-- band at ca. 890 cm-1. The product hadan Act[O] content of 2.65%.

EXAMPLE 7 Preparation of 3-Hydroxy-1,1-dimethylbutylPeroxy-(2-methylbenzoate) (I-7)

A jacketed reactor equipped with a stirrer, a thermometer and anaddition funnel was charged with 19.8 g (0.110 mole) of 74.4%3-hydroxy-1,1-dimethylbutyl hydroperoxide and 30.9 g (0.110 mole) of 20%aqueous KOH solution at 15° C. The resulting solution was washed twicewith 40 g portions of toluene and twice with 40 mL portions of pentane.Then 25 g of water and 50 mL of pentane were added to the aqueoussolution and the solution was cooled to 0°-5° C. Then to the vigorouslystirred reaction mass at 0°-5° C. was added a solution of 7.7 g (0.050mole) of 100% 2-methylbenzoyl chloride and 50 mL of pentane over aperiod of 5 minutes. The resulting mixture was stirred for an additional15 minutes at 0°-5° C. after which stirring was stopped and the reactionmass was allowed to separate into liquid phases. The lower aqueous layerwas removed and discarded. The pentane solution was then washed twice at10° C. with 40 g portions of 10% aqueous KOH solution and then twicewith 20 g portions of saturated aqueous NaHCO₃. All during the work-up apentane insoluble organic layer was carried along. This layer wasdissolved in 50 mL of methylene chloride, dried over anhydrous MgSO₄and, after separation of the spent desiccant by filtration, themethylene chloride was removed in vacuo leaving 6.1 g (48% of theory,uncorrected) of a clear, colorless oil. The pentane solution was thendried over 10% by weight of anhydrous MgSO₄. After separation of thespent desiccant by filtration, the pentane was removed in vacuo leaving3.1 g (25% of theory, uncorrected) of a clear, colorless liquid.Infrared spectra of the two products showed that the two were identical,therefore, they were combined. An infrared spectrum of the combinedproduct showed a strong OH band at ca. 3475 cm-1, a very strongperoxyester carbonyl band at ca. 1740 cm-1 and an --OO-- band at ca. 820cm-1. No ester band was observed at about 1700 cm-1, hence, noester-peroxyester was present in the product. The product had an Act[O]content of 6.28%. Based on a theoretical Act[O] of 6.34% for the desiredtitle product, the assay was 99.5% and the corrected yield was 72.7%.The half-life of I-7 at 100° C. in alpha-methylstyrene (0.20 molar inI-7) was found to be 4.05 hours, therefore, the 10 hour half-lifetemperature for I-7 was estimated to be about 94° C. t-Butylperoxy-(2-methylbenzoate), a commercial peroxyester similar to I-7, wasfound to have a 100° C. half-life in benzene (0.20 molar) of 8.7 hoursand a 10 hour half-life temperature of about 99° C. Therefore, I-7 wassignificantly more active than was t-butyl peroxy-(2-methylbenzoate)based on decomposition data.

EXAMPLE 8 Preparation of 3-Hydroxy-1,1-dimethylbutylPeroxy-(2-chlorobenzoate) (I-8)

A jacketed reactor equipped with a stirrer, a thermometer and anaddition funnel was charged with 20.1 g (0.110 mole) of 73.4%3-hydroxy-1,1-dimethylbutyl hydroperoxide and 30.9 g (0.110 mole) of 20%aqueous KOH solution at 15° C. The resulting solution was washed twicewith 40 g portions of methylene chloride. Then 25 g of water and 50 mLof methylene chloride were added to the aqueous solution and thesolution was cooled to 0°-5° C. To the vigorously stirred reaction massat 0°-5° C. was added a solution of 9.2 g (0.050 mole) of 95%2-chlorobenzoyl chloride and 50 mL of methylene chloride over a periodof 5 minutes. The resulting mixture was stirred for an additional 20minutes at 0°-5° C. after which stirring was stopped and the reactionmass was allowed to separate into liquid phases. The upper aqueous layerwas removed and discarded. The methylene chloride solution was thenwashed twice at 10° C. with 40 g portions of 10% aqueous KOH solutionand then twice with 40 g portions of saturated aqueous NaHCO₃. Themethylene chloride solution was then dried over anhydrous MgSO₄ and,after separation of the spent desiccant by filtration, the methylenechloride was removed in vacuo leaving 11.8 g (86.7% of theory,uncorrected) of a clear, colorless liquid. An infrared spectrum of theproduct showed a strong OH band at ca. 3480 cm-1 and a very strongperoxyester carbonyl band at ca. 1740 cm-1. No ester band was observedat about 1700 cm-1, hence, no ester-peroxyester was present in theproduct. The product had an Act[O] content of 5.23%. Based on atheoretical Act[O] of 5.87% for the desired title product, the assay was89.1% and the corrected yield was 77.2%.

EXAMPLE 9 Preparation of 3-Hydroxy-1,1-dimethylbutylPeroxy-(2-bromobenzoate) (I-9)

The same process and work-up procedure as used in Example 8 was employedin this example. Reacted at 15° C. were 20.1 g (0.110 mole) of 73.4%3-hydroxy-1,1-dimethylbutyl hydroperoxide, 30.9 g (0.110 mole) of 20%aqueous KOH solution, 25 g of water and 11.2 g (0.05 mole) of 98%2-bromobenzoyl chloride. Obtained after the work-up was 14.8 g (93.1% oftheory, uncorrected) of a clear, colorless liquid. An infrared spectrumof the product showed a strong OH band at ca. 3480 cm-1 and a verystrong peroxyester carbonyl band at ca. 1740 cm-1. No ester band wasobserved at about 1700 cm-1, hence, no ester-peroxyester was present inthe product. The product had an Act[O] content of 4.41%. Based on atheoretical Act[O] of 5.04% for the desired title product, the assay was87.5% and the corrected yield was 81.5%.

EXAMPLE 10 Preparation of 3-Hydroxy-1,1-dimethylbutylPeroxy-(2-acetoxybenzoate) (I-10)

The same process and work-up procedure as used in Example 8 was employedin this example. Reacted at 15° C. were 20.1 g (0.110 mole) of 73.4%3-hydroxy-1,1-dimethylbutyl hydroperoxide, 65.0 g (0. 115 mole) of 10%aqueous KOH solution and 10.1 g (0.05 mole) of ca. 98% 2-acetoxybenzoylchloride. Obtained after the work-up was 4.6 g (31% of theory,uncorrected) of a clear, yellow liquid. An infrared spectrum of theproduct showed a strong OH band at ca. 3400 cm-1, a very strongperoxyester carbonyl band at ca. 1730 cm-1 and an ester carbonyl band atabout 1700 cm-1. The ester band observed at about 1700 cm-1 was due tothe acetoxy group in the desired product.

EXAMPLE 11 Reaction of 3-Hydroxy-1,1-dimethylbutyl Hydroperoxide withBenzoyl Chloride

A jacketed reactor equipped with a stirrer, a thermometer and anaddition funnel was charged with 29.7 g (0.20 mole) of 90.3%3-hydroxy-1,1-dimethylbutyl hydroperoxide and 44.0 g (0.22 mole) of 20%aqueous NaOH solution at 20°-25° C. To the vigorously stirred reactionmass at 25°-30° C. was slowly added a solution of 14.1 g (0.10 mole) of100% benzoyl chloride over a period of 20 minutes. The resulting mixturewas stirred for an additional 180 minutes at 25°-30° C. after which 50mL of water and 100 mL of methylene chloride were added. Stirring wasstopped and the reaction mass was allowed to separate into liquidphases. The lower aqueous layer was removed and discarded. The organicsolution was then washed once with 25 mL of water, once with about 25 mLof buffered Na₂ SO₃ solution (i.e., 22 g of water, 1.5 g of sodiumacetate, 1.0 g of acetic acid and 0.63 g of sodium sulfite) and oncewith 25 mL of 7.7% aqueous NaHCO₃ solution. All washes were carried outat 20°-25° C. The methylene chloride solution was then dried over 10% byweight of anhydrous MgSO₄. After separation of the spent desiccant byfiltration, the solvent was removed in vacuo leaving 17.5 g (73.5% oftheory, uncorrected) of a liquid product. The product had a peroxyesterAct[O] content of 3.76%. The product obtained in this example was3-benzoyloxy-1,1-dimethylbutyl peroxybenzoate (C- 1a). The assay of C-1awas 80.5% and the corrected yield was 82.4%. C-la is thebenzoate-peroxybenzoate disclosed in Example 3 of U.S. Pat. No.3,236,872 (Ref. 1). This reference teaches that reactions of benzoylchlorides and acetyl chloride with 3-hydroxy-1,1-dimethylbutylhydroperoxide results in formation of ester-peroxyesters. In the instantexample the skewing of the process conditions in favor of formation of3-hydroxy-1,1-di-methylbutyl peroxybenzoate (C-1, a hydroxyalkylperoxybenzoate), by employing excess 3-hydroxy-1,1-dimethylbutylhydroperoxide failed to result in formation of C-1, but instead, C-1awas formed. Contrary to the above finding, we surprisingly andunexpectedly found that, under essentially the same process conditionsas employed in Example 11, hindered benzoyl chlorides, such as2-chlorobenzoyl chloride, 2-methylbenzoyl chloride, 2-bromobenzoylchloride and 2-acetoxybenzoyl chloride, resulted in formation of thecorresponding hydroxyalkyl substituted peroxybenzoates (see CompositionsI-7, I-8, I-9 and I-10, Examples 7, 8, 9 and 10). These results aretabulated in the table below.

    ______________________________________                                        REACTION PRODUCTS FROM REACTION OF                                            BENZOYL CHLORIDES WITH                                                        3-HYDROXY-1,1-DIMETHYLBUTYL HYDROPEROXIDE                                                     Type(1)  Type of                                              Example                                                                              Product  Product  Benzoyl Chloride                                                                           Assay %                                 ______________________________________                                        7      I-7      H-P      Hindered (2-methyl)                                                                        99.5                                    8      I-8      H-P      Hindered (2-chloro)                                                                        89.1                                    9      I-9      H-P      Hindered (2-bromo)                                                                         87.5                                    10     I-10     H-P      Hindered (2-acetoxy)                                                                       --                                      11     C-1a     E-P      Non-Hindered 80.5                                    ______________________________________                                         (1)H-P  HydroxyPeroxyester                                                    EP  EsterPeroxyester                                                     

EXAMPLE 12 Preparation of OO-t-Butyl O-(2-Hydroxypropyl)Monoperoxyphthalate (I-11)

A 300 mL 3-neck round-bottom flask, equipped with a magnetic stirrer, athermometer, a cold water condenser and an addition funnel, was chargedwith 100 mL of methyl t-butyl ether, 16.7 g (0.06 mole) of 91.3% of2-(t-butylperoxycarbonyl)benzoyl chloride and 5.5 g (0.07 mole) ofpyridine. To this vigorously stirred solution at 20° C. was added 22.8 g(0.30 mole) of 1,2-propanediol over a period of 20 minutes. During theaddition there was a slight exotherm and a white precipitate formed. Thereaction mass was warmed to 25° C. and stirred at 25° C. for 240minutes. The precipitate was separated by filtration and the white solidwas washed with about 25 mL of methyl t-butyl ether. The methyl t-butylether washings were combined with the filtrate and the filtrate waswashed twice with 50 mL portions of 5% aqueous HCl solution, then twicewith 50 mL portions of 3% aqueous NaHCO₃ solution. The methyl t-butylether solution was then dried over 10% by weight of anhydrous MgSO₄ and,after separation of the spent desiccant by filtration, the solvent wasremoved in vacuo leaving 17.4 g (98.3% of theory, uncorrected) of astraw-color liquid. An infrared spectrum of the product showed a strongOH band at ca. 3500 cm-1 and two carbonyl bands at ca. 1720 cm-1 and1770 cm-1. The product had a peroxyester Act[O] content of 5.02%. Basedon a theoretical Act[O] of 5.40% for the desired title product, theassay was 93.0% and the corrected yield was 91.4%.

EXAMPLE 13 Preparation of OO-t-Butyl O-(2-Hydroxypropyl)Monoperoxysuccinate (I-12)

A 250 mL 3-neck round-bottom flask, equipped with a magnetic stirrer, athermometer, a cold water condenser and an addition funnel, was chargedwith 50 mL of methylene chloride, 4.2 g (0.052 mole) of pyridine and19.0 g (0.25 mole) of 1,2-propanediol. The resulting vigorously stirredsolution was cooled to 10° C. and to it was slowly added a solution of11.5 g (0.050 mole) of 94% 3-(t-butylperoxycarbonyl)propionyl chloridein 10 mL of methylene chloride over a period of 20 minutes. The reactionmass was warmed to 20° C. and stirred at 20° C. for 210 minutes. Thereaction mixture was washed at 10°-15° C. with 50 mL of aqueous 5% HClsolution and then twice with 100 mL portions of 5% aqueous NaHCO₃solution. The methylene chloride solution was then dried over 10% byweight of anhydrous MgSO₄ and, after separation of the spent desiccantby filtration, the solvent was removed in vacuo leaving 12.4 g (100% oftheory, uncorrected) of a straw-color liquid. An infrared spectrum ofthe product showed a strong OH band, a strong and broad carbonyl band atca. 1720-1780 cm-1 and a strong --OO-- band at ca. 850 cm-1. The producthad a peroxyester Act[O] content of 6.29%. Based on a theoretical Act[O]of 6.45% for the desired title product, the assay was 97.5% and thecorrected yield was 97.5%.

EXAMPLE 14 Preparation of2-Methoxy-2-(3-hydroxy-1,1-dimethylbutylperoxy)propane (I-13)

A 250 mL 3-neck round-bottom flask, equipped with a magnetic stirrer, athermometer, a cold water condenser and an addition funnel, was chargedwith 100 mL of methylene chloride and 3.6 g (0.050 mole) of methylisopropenyl ether. To this solution at 20°-5° C. was slowly added 8.0 g(0.053 mole) of dry, 88.4% 3-hydroxy-1,1-dimethylbutyl hydroperoxideover a period of about 30 minutes. The reaction mass was warmed to 35°C. and stirred at 35° C. for 150-180 minutes. The reaction mass waswashed twice with 50 mL portions of water. The methylene chloridesolution was then dried over 10% by weight of anhydrous MgSO₄ and, afterseparation of the spent desiccant by filtration, the solvent was removedin vacuo leaving 9.2 g (89.3% of theory, uncorrected) of a liquidproduct. An infrared spectrum of the product showed a strong OH band atca. 3500 cm-1 and a small --OO-- band at ca. 870 cm-1. The product hadan Act[O] content of 8.32%. Based on a theoretical Act[O] of 7.76% forthe desired title product, the assay was 100% and the corrected yieldwas 89.3%.

EXAMPLE 15 Preparation of OO-(3-Hydroxy-1,1-dimethylbutyl)O-(2,4-Dioxacyclopentyl)methyl Monoperoxycarbonate (I-14)

In this example the chloroformate of glycerol formal was initiallysynthesized by treating glycerol formal (a mixture of[2,4-dioxacyclopentyl]methanol and 3,5-dioxacyclohexanol) with excessphosgene followed by isolation of the product, a mixture of(2,4-dioxacyclopentyl)methyl chloroformate and 3,5-dioxacyclohexylchloroformate. For the sake of brevity the chloroformate mixture wasreferred to as (2,4-dioxacyclopentyl)methyl chloroformate. Subsequently,(2,4-dioxacyclopentyl)methyl chloroformate was reacted with3-hydroxy-1,1-dimethylbutyl hydroperoxide in the presence of aqueous KOHsolution to form the product, a mixture ofOO-(3-hydroxy-1,1-dimethylbutyl) O-(2,4-dioxacyclopentyl)methylmonoperoxycarbonate and OO-(3-hydroxy-1,1-dimethylbutyl)O-(3,5-dioxacyclohexyl) monoperoxycarbonate (I-14). Again, for the sakeof brevity, the product of this example was referred to asOO-(3-hydroxy-1,1-dimethylbutyl) O-(2,4-dioxacyclopentyl)methylmonoperoxycarbonate rather than the two-component mixture name.

A jacketed reactor equipped with a stirrer, a thermometer and anaddition funnel was charged with 80. mL of methyl t-butyl ether, 47.8 g(0.26 mole) of 73.4% 3-hydroxy-1,1-dimethylbutyl hydroperoxide and 145 g(0.26 mole) of 10% aqueous KOH solution and the mixture was stirred at20° C. The liquid phases were allowed to separate and the lower methylt-butyl ether layer was removed. Then another 80 mL of methyl t-butylether was added, the mixture stirred at 20° C., the liquid layerssettled and the lower methyl t-butyl ether layer removed. This washprocedure was repeated a third time. Then the vigorously stirred aqueoussolution was heated to 24°-28° C. and to it was slowly added (over 45minutes) 59.2 g (0.30 mole) of 98% (2,4-dioxacyclopentyl)methylchloroformate and the resulting mixture was stirred for an additional 90minutes at 25°-30° C. Then 300 mL of methyl t-butyl ether was added,stirring was terminated and the lower aqueous layer was separated fromthe organic phase and discarded. The product solution was then washed at20° C. twice with 100 g portions of 10% aqueous KOH solution, thenseveral times with 100 mL portions of water in order to adjust the pH toabout 7. The methyl t-butyl ether solution was then dried over 10% byweight of anhydrous MgSO4. After separation of the spent desiccant byfiltration, the methyl t-butyl ether was removed in vacuo leaving 7.2 g(14% of theory, uncorrected) of a light, straw-colored liquid. Aninfrared spectrum of the product showed a strong OH band at ca. 3400cm-1, an unresolved double carbonyl band at ca. 1790 cm-1 and 1740 cm-1and a small --OO-- band at ca. 840 cm-1. The product contained 1.7%3-hydroxy-1,1-dimethylbutyl hydroperoxide and had a monoperoxycarbonateAct[O] content of 4.99%. Based on a theoretical Act[O] of 6.05% for thedesired title product mixture, the assay was 82.5% and the correctedyield was 11.2%.

EXAMPLE 16 Preparation of OO-(3-Hydroxy-1,1-dimethylbutyl)O-(3,3-Dimethyl-2,4-dioxacyclopentyl)methyl Monoperoxycarbonate (I-15)

In this example the chloroformate of solketal was initially synthesizedby treating solketal (a mixture of [3,3-dimethyl-2,4-dioxacyclopentyl]methanol and 4,4-dimethyl-3,5-dioxacyclohexanol) with excess phosgenefollowed by isolation of the product, a mixture of(3,3-dimethyl-2,4-dioxacyclopentyl)methyl chloroformate and4,4-dimethyl-3,5-dioxacyclohexyl chloroformate. For the sake of brevitythe chloroformate mixture was referred to as(3,3-dimethyl-2,4-dioxacyclopentyl)methyl chloroformate. Subsequently,(3,3-dimethyl-2,4-dioxacyclopentyl)methyl chloroformate was reacted with3-hydroxy-1,1-dimethylbutyl hydroperoxide in the presence of aqueous KOHsolution to form the product, a mixture ofOO-(3-hydroxy-1,1-dimethylbutyl)O-(3,3-dimethyl-2,4-dioxacyclopentyl)methyl monoperoxycarbonate andOO-(3-hydroxy-1,1-dimethylbutyl) O-(4,4-dimethyl-3,5-dioxacyclohexyl)monoperoxycarbonate (I-15). Again, for the sake of brevity, the productof this example was referred to as OO-(3-hydroxy-1,1-dimethylbutyl)O-(3,3-dimethyl-2,4-dioxacyclopentyl)methyl monoperoxycarbonate ratherthan the two-component mixture name.

A jacketed reactor equipped with a stirrer, a thermometer and anaddition funnel was charged with 50 mL of methylene chloride, 25.6 g(0.14 mole) of 73.4% 3-hydroxy-1,1-dimethylbutyl hydroperoxide and 62.7g (0.14 mole) of 12.5% aqueous KOH solution and the mixture was stirredat 20°-25° C. The liquid phases were allowed to separate and the lowermethylene chloride layer was removed. Then another 50 mL of methylenechloride was added, the mixture stirred at 20°-25° C., the liquid layerssettled and the lower methylene chloride layer was removed. Then thevigorously stirred aqueous solution was heated to 23°-28° C. and to itover 20 minutes was slowly added 19.7 g (0.10 mole) of 98.7%(3,3-dimethyl-2,4-dioxacyclopentyl)methyl chloroformate and theresulting mixture was stirred for an additional 90 minutes at 25° C.Then 100 mL of methyl t-butyl ether was added, stirring was terminatedand the lower aqueous layer was separated from the organic phase anddiscarded. The product solution was then washed at 20° C. twice with 50g portions of 10% aqueous KOH solution, then several times with 50 mLportions of water in order to adjust the pH to about 7. The methylt-butyl ether solution was then dried over 10% by weight of anhydrousMgSO4. After separation of the spent desiccant by filtration, the methylt-butyl ether was removed in vacuo leaving 13.0 g (44% of theory,uncorrected) of a colorless liquid. An infrared spectrum of the productshowed a strong OH band at ca. 3390 cm-1, an unresolved double carbonylband at ca. 1790 cm-1 and 1745 cm-1 and a small --OO-- band at ca. 835cm-1. The product contained 0.2% 3-hydroxy-1,1-dimethylbutylhydroperoxide and had a monoperoxycarbonate Act[O] content of 5.27%.Based on a theoretical Act[O] of 5.47% for the desired title productmixture, the assay was 96.3% and the corrected yield was 42.7%.

EXAMPLE 17 Preparation of OO-(3-Hydroxy-1,1-dimethylbutyl)O-(2,3-Dihydroxypropyl) Monoperoxycarbonate (I-16)

In this example the product mixture of Example 16, i.e., I-15, a mixtureof OO-(3-hydroxy-1,1-dimethylbutyl)O-(3,3-dimethyl-2,4-dioxacyclopentyl)methyl monoperoxycarbonate andOO-(3-hydroxy-1,1-dimethylbutyl) O-(4,4-dimethyl-3,5-dioxacyclohexyl)monoperoxycarbonate, was treated with dilute aqueous hydrochloric acidsolution to form the desired product mixture, I-16, consisting ofOO-(3-hydroxy-1,1-dimethylbutyl) O-(2,3-dihydroxypropyl)monoperoxycarbonate and OO-(3-hydroxy-1,1-dimethylbutyl)O-(1,3-dihydroxy-2-propyl) monoperoxycarbonate. For the sake of brevity,the product of this example was referred to asOO-(3-hydroxy-1,1-dimethylbutyl) O-(2,3-dihydroxypropyl)monoperoxycarbonate rather than the two-component mixture name.

A flask equipped with a magnetic stirrer and a thermometer was chargedwith 5.0 g (0.0165 mole) of 96.3% OO-(3-hydroxy-1,1-dimethylbutyl)O-(3,3-dimethyl-2,4-dioxacyclopentyl)methyl monoperoxycarbonate (I-15)and 5.0 g (0.0068 mole) of 5% aqueous hydrochloric acid solution at20°-25° C. The resulting mixture was stirred at 20°-25° C. for 240minutes. Then excess solid sodium carbonate (ca. 1.0 g) was added inorder to neutralize the hydrochloric acid. About 150 mL of acetone wasadded to the neutralized reaction mass and the solid sodium salts thatformed (NACl and Na₂ CO₃) were separated by filtration. The acetone andwater were removed in vacuo at room temperature. While the .acetone andwater were being removed, additional inorganic sodium salts precipitatedand had to be removed by filtration. Obtained was 4.0 g (96% of theory,uncorrected) of a colorless liquid. An infrared spectrum of the productshowed a strong and broad OH band at ca. 3400 cm-1, an unresolved doublecarbonyl band at ca. 1775 cm-1 and 1740 cm-1 and a small --OO-- band atca. 830 cm-1. The OH band at 3400 cm-1 for the product of this example(I-16) was significantly broader and deeper than the OH band at 3390cm-1 for the starting material, I-15. In addition, the IR spectra of thestarting material (I-15) and the product (I-16) were significantlydifferent in the 700-1500 cm-1 spectral region. The product contained8.4% 3-hydroxy-1,1-dimethylbutyl hydroperoxide and had amonoperoxycarbonate Act[O] content of 4.74%. Based on a theoreticalAct[O] of 6.34% for the desired title product mixture, the assay was74.8% and the corrected yield was 71.9%. The IR spectral data and theAct [0] data confirmed that the product obtained in this example was thedesired title product mixture, I-16.

EXAMPLE 18 SPI Exotherms of Hydroxy-Peroxides

The unsaturated polyester resin composition employed in this example wasa mixture of an unsaturated polyester and styrene monomer. Theunsaturated polyester was an alkyd resin made by esterifying thefollowing components:

    ______________________________________                                        Component       Quantity (moles)                                              ______________________________________                                        Maleic Anhydride                                                                              1.0 moles                                                     Phthalic Anhydride                                                                            1.0 moles                                                     Propylene Glycol                                                                              2.2 moles                                                     ______________________________________                                    

To the resulting resin was added 0,013% by weight of hydroquinoneinhibitor. The alkyd resin had an Acid No. of 45-50. Seven (7) parts byweight of the above unsaturated polyester alkyd was diluted with three(3) parts by weight of monomeric styrene. The resulting unsaturatedpolyester resin composition had the following properties:

a. Viscosity (Brookfield No. 2 at 20 r.p.m.): 13.0 poise

b. Specific gravity: 1.14

CURING PROCEDURE

Gelation and cure characteristics of the initiator tested weredetermined using a conventional SPI Exotherm Procedure ("SUGGESTED SPIPROCEDURE--Procedure for Running Exotherm Curves--Using ThermocoupleNeedle, 24th Annual Technical Conference, 1969, ReinforcedPlastics/Composites Division, the Society of the Plastics Industry,Inc., page 6"),

Using the procedure at 138° C. (280° F.)OO-(3-hydroxy-1,1-dimethylbutyl) O-isopropyl monoperoxycarbonate (I-3),a hydroxy-monoperoxycarbonate of the instant invention, and OO-t-butylO-(2-ethylhexyl) monoperoxycarbonate (A-1), a monoperoxycarbonate of theart, were evaluated. The results are summarized in Table 15-1 and showthat I-3, a composition of the instant invention was active in gellingand curing the unsaturated polyester resin.

                  TABLE 18-1                                                      ______________________________________                                        SPI Exotherm Data at 138° C.                                           Curing Level,     Gel,    Cure, Peak Exo-                                                                             Barcol                                Catalyst                                                                             %          mins    mins  therm, °F.                                                                     Hardness                              ______________________________________                                        A-1    0.75       1.9     2.6   450     40-45                                 I-3    0.72 (1)   2.2     3.0   459     35-40                                 ______________________________________                                         (1) Equivalent Act [O] level to that of 0.75 phr of A1                   

Also, OO-t-butyl O-(2-hydroxypropyl) monoperoxyphthalate (I-11), ahydroxy-peroxyester of the instant invention, and t-butyl peroxybenzoate(A-2), a peroxyester of the art, were evaluated using this procedure.The temperature employed was 100° C. (212° F.). The results aresummarized in Table 15-2 and show that I-11, a composition of theinstant invention, was active in gelling and curing the unsaturatedpolyester resin.

                  TABLE 18-2                                                      ______________________________________                                        SPI Exotherm Data at 100° C.                                           Curing  Level,  Gel,    Cure,  Peak Exo-                                                                             Barcol                                 Catalyst                                                                              %       mins    mins   therm, °F.                                                                     Hardness                               ______________________________________                                        A-2     1.0     8.0     10.5   390     50                                     I-11    1.0     9.4     13.7   364     45-50                                  ______________________________________                                    

Also evaluated using the procedure were 3-hydroxy-1,1-dimethylbutylperoxy-(2-methylbenzoate) (I-7), a hydroxyperoxyester of the instantinvention, and t-butyl peroxybenzoate (A-2), a peroxyester of the art.The temperature employed was 115° C. (239° F.). The results aresummarized in Table 15-3 and show that I-7, a composition of the instantinvention, was surprisingly more active in gelling and curing theunsaturated polyester resin than was A-2, a peroxyester of the art.

                  TABLE 18-3                                                      ______________________________________                                        SPI Exotherm Data at 115° C.                                           Curing Level,     Gel,   Cure, Peak Exo-                                                                              Barcol                                Catalyst                                                                             %          mins   mins  therm, °F.                                                                      Hardness                              ______________________________________                                        A-2    1.0        4.4    5.5   436      40-45                                 I-7    1.0        2.3    3.3   436      40-45                                 I-7    1.3 (1)    2.0    2.8   413      40-45                                 ______________________________________                                         (1) Equivalent Act [O] level to that of 1.0 phr of A2                    

What is claimed:
 1. In a process for curing an unsaturated polyesterresin composition comprising heating such resins at appropriatetemperatures in the presence of initiating amounts of peroxides, theimprovement comprising the use in such process of hydroxy peroxideshaving the structure A:

    HO--R.sub.11 --X--OO--R                                    (A)

wherein X is a direct bond or the diradical: ##STR22## and wherein: WhenX is a direct bond: R is selected from the structures: ##STR23##wherein: R₁ is a lower alkyl radical of 1 to 4 carbons, an alkoxyradical of 1 to 4 carbons, a phenyl radical, an acyloxy radical of 2 to8 carbons, a t-alkylperoxycarbonyl radical of 5 to 9 carbons, hydroxy,fluoro, chloro or bromo, R'₁ is H or is selected from the same radicalsas R₁, and may be the same as or different than R₁ ; n is 0 or 1; R₂ isa substituted or unsubstituted alkyl radical of 1 to 18 carbons,substituents being one or more alkyl radicals of 1 to 6 carbons,t-alkylperoxy radicals of 4 to 8 carbons, alkoxy radicals of 1 to 6carbons, aryloxy radicals of 6-10 carbons, hydroxy, chloro, bromo orcyano; R₂ is a substituted or unsubstituted cycloalkyl radical of 5 to12 carbons, a substituted or unsubstituted 4-piperidinyl radical, or asubstituted or unsubstituted 1,3-dioxan-5-yl radical with substituentsfor the cycloalkyl, piperidinyl or dioxanyl radicals being one or morelower alkyl radicals of 1 to 4 carbons; or R₂ is the radical: ##STR24##wherein z is 0 or 1, R_(a), R_(b) and R_(c) are the same or differentand are H-- or alkyl radicals of 1 to 8 carbons, or R_(a) and R_(b) canbe connected forming together with the carbon atoms to which they areattached a substituted or unsubstituted ring containing 5-12 carbons,substituents being one or more alkyl radicals of 1 to 5 carbons orphenyl radicals; R₂₂ is a substituted or unsubstituted alkylenediradical of 2 to 3 carbons, substituents being one or more lower alkylradicals of 1 to 4 carbons, or a substituted or unsubstituted1,2-phenylene diradical, substituents being one or more lower alkylradicals of 1 to 4 carbons, chloro, bromo, nitro or carboxy; R₃ is alower alkyl radical of 1 to 4 carbons, or the two R₃ radicals can beconnected together forming together with the carbon atom to which theyare attached a ring containing 5 to 6 carbons; R₄ is a lower alkylradical of 1 to 4 carbons; the R₁₁ diradical is the structure, ##STR25##wherein R₅ is a lower alkyl radical of 1 to 4 carbons; and R₃₃ is asubstituted or unsubstituted alkylene diradical of 2 to 4 carbons,substituents being one or more lower alkyl radicals of 1 to 4 carbons,with the proviso that when n is 0 and R₃₃ is an alkylene diradical of 2carbon atoms substituted with methyl on the C atom alpha to the hydroxygroup, R₂ is not a unsubstituted alkyl radical of 1 to 9 carbon atoms oran alkyl radical of 1 to 9 carbon atoms substituted with one or morelower alkyl radicals of 1 to 6 carbon atoms; andII. when X is thediradical: ##STR26## Y is oxy or --NR₆ --, wherein R₆ is H or asubstituted or unsubstituted alkyl radical of 1 to 8 carbons,substituents being one or more lower alkyl radicals of 1 to 4 carbons orhydroxy, and R₂₂ is as defined above; R is a substituted orunsubstituted t-alkyl radical of 4 to 12 carbons, a cumyl radical or acumyl radical substituted with lower alkyl radicals said lower alkylradicals totaling 1 to 4 carbon atoms, substituents for the t-alkylradical being lower alkyl radicals of 1 to 4 carbons or a t-alkylperoxyradical of 4 to 8 carbons; and R₁₁ is a substituted or unsubstitutedalkylene diradical of 2 to 8 carbons, substituents being one or morelower alkyl radicals of 1 to 4 carbons lower hydroxyalkyl radicals of 1to 4 carbons or hydroxy.
 2. The process of claim 1, wherein the curingagent is selected from the group consisting ofOO-(3-hydroxy-1,1-dimethylbutyl) O-isopropyl monoperoxycarbonate,3-hydroxy-1,1-dimethylbutyl peroxy-(2-methylbenzoate) and OO-t-butylO-(2-hydroxypropyl)monoperoxyphthalate.